CN111029552B - A high voltage and high rate lithium cobalt oxide cathode material and preparation method thereof - Google Patents

A high voltage and high rate lithium cobalt oxide cathode material and preparation method thereof Download PDF

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CN111029552B
CN111029552B CN201911347332.6A CN201911347332A CN111029552B CN 111029552 B CN111029552 B CN 111029552B CN 201911347332 A CN201911347332 A CN 201911347332A CN 111029552 B CN111029552 B CN 111029552B
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李雪华
吕菲
徐宁
李琪
吴孟涛
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Tianjin B&M Science and Technology Co Ltd
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Abstract

本发明公开了一种高电压高倍率钴酸锂正极材料及其制备方法，钴酸锂材料表面导电氧化物的包覆在一定程度上阻止了钴酸锂本体材料和电解液的直接接触，抑制了电解液在高电压下的氧化的副反应，从而提升了钴酸锂界面在高电压下的稳定性，改善了材料的循环稳定性。此外，将钴酸锂材料表面通过导电氧化物进行包覆，颗粒表面形成的导电网络通过导电剂与集流体相连提升了钴酸锂颗粒表面的电子导电率，增加了电化学反应的活性面积，降低了其传荷阻抗，从而增加了充放电时的电化学反应活性；更重要的是，按特定比例得到的复合导电氧化物包覆层由于离子间化学键合力将导致这种复合包覆层具有更稳定的结构，有利于提升材料的倍率性能和稳定性。

Figure 201911347332

The invention discloses a high-voltage and high-rate lithium cobalt oxide positive electrode material and a preparation method thereof. The coating of the conductive oxide on the surface of the lithium cobalt oxide material prevents the direct contact between the lithium cobalt oxide body material and the electrolyte to a certain extent, and inhibits the direct contact between the lithium cobalt oxide material and the electrolyte. The side reaction of the oxidation of the electrolyte at high voltage is eliminated, thereby improving the stability of the lithium cobalt oxide interface at high voltage and improving the cycle stability of the material. In addition, the surface of the lithium cobalt oxide material is coated with a conductive oxide, and the conductive network formed on the surface of the particle is connected to the current collector through a conductive agent, which improves the electronic conductivity of the surface of the lithium cobalt oxide particle and increases the active area of the electrochemical reaction. It reduces its charge transfer resistance, thereby increasing the electrochemical reactivity during charging and discharging; more importantly, the composite conductive oxide coating layer obtained in a specific proportion will cause this composite coating layer to have a chemical bonding force between ions. A more stable structure is beneficial to improve the rate performance and stability of the material.

Figure 201911347332

Description

High-voltage high-rate lithium cobalt oxide cathode material and preparation method thereof
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a high-voltage high-rate lithium cobalt oxide positive electrode material and a preparation method thereof.
Background
With the rapid development of 3C mobile electronic devices represented by smart phones, notebook computers, digital cameras, and the like, extremely high requirements are put forward on the performance of lithium ion battery materials. Lithium cobaltate (LiCoO)2) The lithium ion battery positive electrode material is a mainstream positive electrode material of the current 3C electronic product and still occupies an irreplaceable position in the field of the positive electrode material of the lithium ion battery. LiCoO2Albeit with up to 274mAh g-1But only 140mAh g can be discharged in practical application-1The reason for the discharge capacity is that lithium ions are desorbed when the battery is charged to 4.2V or moreThe amount exceeded 50%, and the reversible capacity dropped rapidly. At present, with the development of electronic products, the requirement on the energy density of a battery is higher, and for lithium cobaltate, although the specific capacity of the lithium cobaltate can be improved by increasing the charge cut-off voltage of a lithium cobaltate material, the cycle and rate performance of the lithium cobaltate are reduced, so that the lithium cobaltate material needs to be modified.
In the modification method of lithium cobaltate, the ion doping of the bulk phase can improve the stability of the bulk phase structure, but can not inhibit the side reaction in the process of charging and discharging the lithium cobaltate; the surface coating modification method can improve the stability of the interface and the bulk phase crystal structure of the lithium cobaltate in the circulation process. At present, most of materials commonly used for coating and modifying the surface of lithium cobaltate are electronic or lithium ion insulator materials, and the lithium cobaltate materials show semiconductor characteristics after certain lithium is removed, so the electron and lithium ion conduction performance of the surface of lithium cobaltate particles is influenced by the insulator coating, and the electrochemical performance of the lithium cobaltate materials is limited. Therefore, a proper coating material needs to be selected to achieve a good comprehensive effect.
Conductive oxides such as tin-doped indium oxide (ITO), aluminum-doped zinc oxide (AZO), and fluorine-doped tin oxide (FTO) have good self-stability under the premise of chemical stability, and are often used as modified coating materials for positive electrode materials. The Chinese patent CN106803586A adopts ITO coated ternary/lithium iron phosphate to prepare the anode material, and the capacity retention rate of the material is obviously improved; the Chinese patent CN104241635A adopts AZO to coat and prepares the AZO-coated complex lithium oxide material.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a high-voltage high-rate lithium cobalt oxide positive electrode material and a preparation method thereof, the method is simple, a better coating layer can be obtained through heat conduction treatment in the coating modification process, the exchange of metal ions in the coating layer and ions in the lithium cobalt oxide plays a certain doping role, the structure of the material is improved, and the stability of an interface and a bulk crystal structure of the lithium cobalt oxide in the circulation process is improved, so that better electrochemical performance is obtained.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a high-voltage high-rate lithium cobalt oxide positive electrode material comprises the following steps:
1) preparation of lithium cobaltate material
Mixing Li in a molar ratio of Li/Co of 1.03-1.072CO3And Co3O4Uniformly mixing, carrying out high-temperature reaction in a bell-type furnace, presintering at 950 ℃ for 4-6 h, then increasing the temperature, continuously calcining at 1000-1100 ℃ for 6-14 h, cooling to room temperature along with the furnace, and crushing to obtain a pre-product; uniformly mixing the crushed pre-product with an additive in proportion, calcining for 4-7 hours at 900-950 ℃, and crushing to obtain lithium cobaltate powder;
2) preparation of conductive oxide coating solution by sol-gel method
Dissolving a metal salt A in a mixed solution of water and ethanol, adding a metal salt B after the metal salt A is completely dissolved, stirring in a water bath at 50-70 ℃ to fully dissolve the metal salt B to obtain a clear and transparent solution, cooling, adding ethanol to prepare a conductive oxide coating solution with the concentration of 0.1mol/L, and standing the prepared coating solution at room temperature for 24 hours for later use; wherein the molar ratio of the metal salt A to the metal salt B is 2-20: 1, and the volume ratio of a mixed solution of water and ethanol is 1: 10-30;
3) coating of
Weighing 3-8 g of prepared lithium cobaltate powder, adding the prepared coating solution in the step 2), wherein the addition amount of the coating solution is 0.5-4 wt% of the conductive oxide/lithium cobaltate, based on the net content of the conductive oxide in the coating solution, fully stirring at room temperature, and heating until the solvent is completely evaporated; and sintering for 5-8 h at 500-700 ℃ to obtain the coated and modified lithium cobaltate positive electrode material.
The additive is one or more of magnesium oxide, magnesium hydroxide, titanium dioxide, cerium oxide, aluminum oxide and zirconium chloride. Each of said additives being Li2CO3And Co3O40.03-0.2% of the total mass.
The metal salt A is one or more of soluble zinc salt, tin salt and indium salt; the metal salt B is one or more of soluble aluminum salt, fluorine salt, tin salt and antimony salt; when the metal salt A or the metal salt B is multiple, a dispersant is required to be additionally added, the dispersant is an alcohol amine substance, and the ratio of the amount of the metal salt A to the amount of the dispersant is 1: 0.3-1.
The conductive oxide prepared in the step 2) is one or more of tin-doped indium oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide and antimony-doped tin dioxide.
The conductive oxide prepared in the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide.
The conductive oxide prepared In the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide, wherein the molar amount of Zn In the aluminum-doped zinc oxide and the molar amount of In the tin-doped indium oxide is as follows: and (3) tin-doped indium oxide being 5-8: 3.
The lithium cobaltate positive electrode material prepared by the preparation method of the high-voltage high-rate lithium cobaltate positive electrode material.
The invention has the beneficial effects that: the method adopts the traditional two-stage method to synthesize the lithium cobaltate, is simple and easy to implement, and dopes the additive into the structure of the lithium cobaltate in the synthesis process so as to ensure the stability of the structure when the lithium cobaltate is subjected to lithium intercalation and deintercalation under high voltage. The conductive oxide is selected to carry out coating modification on the lithium cobaltate material, and not only can play a role of a coating layer, but also the electronic conductivity of the surface of the lithium cobaltate particle can be improved to a certain extent.
Drawings
Fig. 1 is an XRD pattern of comparative example 1 and example 1.
Fig. 2 is SEM images of comparative example 1 and example 1.
Fig. 3 is a graph of cycle performance for comparative example 1 and example 1.
Fig. 4 is a graph of rate performance in comparative example 1 and example 2.
Detailed Description
The method for improving the cycling performance and rate capability of lithium cobaltate under high voltage according to the present invention will be described in more detail with reference to the following examples, but is not limited thereto.
The preparation method of the high-voltage high-rate lithium cobalt oxide positive electrode material comprises the following steps of:
1) preparation of lithium cobaltate material
Mixing Li in a molar ratio of Li/Co of 1.03-1.072CO3And Co3O4Uniformly mixing, carrying out high-temperature reaction in a bell-type furnace, presintering at 950 ℃ for 4-6 h, then increasing the temperature, continuously calcining at 1000-1100 ℃ for 6-14 h, cooling to room temperature along with the furnace, and crushing to obtain a pre-product; uniformly mixing the crushed pre-product with an additive in proportion, calcining for 4-7 hours at 900-950 ℃, and crushing to obtain lithium cobaltate powder;
2) preparation of conductive oxide coating solution by sol-gel method
Dissolving a metal salt A in a mixed solution of water and ethanol, adding a metal salt B after the metal salt A is completely dissolved, stirring in a water bath at 50-70 ℃ to fully dissolve the metal salt B to obtain a clear and transparent solution, cooling, adding ethanol to prepare a conductive oxide coating solution with the concentration of 0.1mol/L, and standing the prepared coating solution at room temperature for 24 hours for later use; wherein the molar ratio of the metal salt A to the metal salt B is 2-20: 1, and the volume ratio of a mixed solution of water and ethanol is 1: 10-30;
3) coating of
Weighing 3-8 g of prepared lithium cobaltate powder, adding the prepared coating solution in the step 2), wherein the addition amount of the coating solution is 0.5-4 wt% of the conductive oxide/lithium cobaltate, based on the net content of the conductive oxide in the coating solution, fully stirring at room temperature, and heating until the solvent is completely evaporated; and sintering for 5-8 h at 500-700 ℃ to obtain the coated and modified lithium cobaltate positive electrode material.
The additive is one or more of magnesium oxide, magnesium hydroxide, titanium dioxide, cerium oxide, aluminum oxide and zirconium chloride. Each of said additives being Li2CO3And Co3O40.03-0.2% of the total mass.
The metal salt A is one or more of soluble zinc salt, tin salt and indium salt; the metal salt B is one or more of soluble aluminum salt, fluorine salt, tin salt and antimony salt; when the metal salt A or the metal salt B is multiple, a dispersant is required to be additionally added, the dispersant is an alcohol amine substance, and the ratio of the amount of the metal salt A to the amount of the dispersant is 1: 0.3-1.
The conductive oxide prepared in the step 2) is one or more of tin-doped indium oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide and antimony-doped tin dioxide.
The conductive oxide prepared in the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide.
The conductive oxide prepared In the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide, wherein the molar amount of Zn In the aluminum-doped zinc oxide and the molar amount of In the tin-doped indium oxide is as follows: and (3) tin-doped indium oxide being 5-8: 3.
The lithium cobaltate positive electrode material prepared by the preparation method of the high-voltage high-rate lithium cobaltate positive electrode material.
The coating of the conductive oxide on the surface of the lithium cobaltate material prevents direct contact between the lithium cobaltate body material and the electrolyte to a certain extent, and inhibits the side reaction of oxidation of the electrolyte under high voltage, so that the stability of a lithium cobaltate interface under high voltage is improved, and the cycling stability of the material is improved. In addition, the surface of the lithium cobaltate material is coated by the conductive oxide, and a conductive network formed on the surface of the particle is connected with the current collector through the conductive agent, so that the electronic conductivity of the surface of the lithium cobaltate particle is improved, the active area of electrochemical reaction is increased, and the load transfer impedance of the electrochemical reaction is reduced, thereby increasing the electrochemical reaction activity during charging and discharging; more importantly, the composite conductive oxide coating layer obtained according to a specific proportion has a more stable structure due to the chemical bonding force among ions, and the rate capability of the material is favorably improved.
The stability of a lithium cobaltate interface under high voltage is improved through the coating of the conductive oxide, and the cycling stability of the material is improved; in addition, the coating of the conductive oxide also improves the conductivity of the surface of the lithium cobaltate particles, thereby increasing the electrochemical reaction activity during charging and discharging and being beneficial to improving the rate capability of the material; in addition, because strong chemical bonding force exists between ions, the structural stability of the material can be obviously improved, and therefore, the composite conductive oxide coating layer obtained by compounding two or more than two conductive oxides according to a proper proportion is beneficial to improving the cycle stability and high rate performance of a lithium cobaltate product.
Comparative example 1
Mixing Li2CO3And Co3O4Uniformly mixing, carrying out a first high-temperature reaction in a bell-type furnace, preburning at 950 ℃ for 6h, then raising the temperature to 1030 ℃, continuously calcining for 7h, cooling to room temperature along with the furnace, uniformly mixing with magnesium oxide, titanium dioxide and aluminum oxide according to the mass ratio of 0.15%, 0.05% and 0.1%, pulverizing, calcining at 950 ℃ for 6h, and pulverizing to obtain the uncoated lithium cobaltate material.
Example 1
The product synthesized in comparative example 1 was used as a raw material, and subjected to coating modification treatment.
Preparing a mixed solution according to the volume ratio of 1:20, and then adding a proper amount of stannous chloride dihydrate (SnCl)2·2H2O), adding Sn after fully dissolving2+And stirring the ammonium fluoride with the molar ratio of 30% in a water bath at 60 ℃ until the ammonium fluoride is fully dissolved to obtain a clear and transparent solution, cooling the solution, metering the volume to 0.1mol/L by using ethanol in a volumetric flask to obtain the fluorine-doped tin oxide coating solution, and standing the solution for 24 hours at room temperature for later use.
5g of lithium cobaltate powder are weighed, and the powder is added according to SnO2And calculating the mass of the fluorine-doped tin oxide coating solution to be 2 wt.%, stirring at room temperature to fully mix the fluorine-doped tin oxide coating solution, heating to 100 ℃ to evaporate the water and ethanol solvent, and finally carrying out heat treatment on the dried mixture at 600 ℃ to obtain the fluorine-doped tin oxide coating modified lithium cobaltate cathode material (sample FTO-LCO).
As can be seen from FIG. 1, the FTO-LCO is only coated with a layer of FTO material on the surface layer, and does not affect the bulk structure of the material. It can also be seen from the SEM photograph of fig. 2 that the coating is relatively uniform.
The fluorine-doped tin oxide coated lithium cobaltate material does not significantly affect the exertion of the capacity of the lithium cobaltate material, has the most stable cycle performance and excellent rate performance, and has the capacity retention rate of 92.8 percent at 0.1 ℃ after 100 cycles within the voltage range of 2.75-4.5V, while the comparative sample 1 is only 67.9 percent, as shown in FIG. 3; and the rate capability is obviously improved,
further investigation of the material under high charge-discharge multiplying power of 4C and 8C shows that the capacity retention rate of FTO-LCO can still reach 85.0% and 78.4%, while the comparative sample is only 58.8% and 45.5%.
Example 2
The product synthesized in the comparative example was used as a raw material, and subjected to coating modification treatment.
Weighing a proper amount of zinc acetate dihydrate (Zn (CH) according to the molar ratio of 7:0.4:3:0.333COO)2·2H2O), aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), indium trichloride tetrahydrate (InCl)3·4H2O) and stannous chloride dihydrate (SnCl)2·2H2O) is added into 1000ml ethanol solution in turn, ethanolamine (NH) is selected2CH2CH2OH) is used as a dispersing agent, the dispersing agent with the mass of zinc acetate dihydrate and the like is added into the solution after stirring, the mixture is placed in a water bath at 50 ℃ and fully stirred until a clear and transparent solution is obtained, the solution is cooled and then is subjected to constant volume to 0.1mol/L by using ethanol in a volumetric flask, namely, the AZO/ITO composite coating solution is obtained, and the prepared solution is kept stand for 24 hours at room temperature for later use.
Weighing 5g of sample LCO powder, adding a composite coating solution with the mass being 2 wt.% calculated according to ZnO, fully stirring and mixing at room temperature, placing the mixture in a water bath at 80 ℃ for continuous heating and stirring until an ethanol solvent is completely evaporated, and finally carrying out heat treatment on the obtained mixture at 600 ℃ to obtain the coating modified lithium cobaltate cathode material (sample AZO/ITO-LCO).
The electrical property test shows that the AZO/ITO composite coating modified lithium cobaltate cathode material shows excellent electrochemical property, and under the test conditions that the charge-discharge multiplying power is 0.5C and the test voltage range is 2.75-4.5V, the capacity retention rate of a sample AZO/ITO-LCO is 98.2% after 50 times of circulation, while the comparative sample LCO is only 83.3%.
The capacity retention rate of the material was tested by changing the charge and discharge rate to 0.1C, 0.5C, 1C, 2C, 4C, 8C, respectively. When the charge-discharge multiplying power is 8C, the capacity retention rate of the comparative sample is only 45.4%, and the capacity retention rate of the AZO/ITO-LCO sample can still reach 86.6%, which is shown in FIG. 4. Compared with the single coating material in example 1, the capacity retention rate of the double coating material at high discharge rate is more excellent, which is probably caused by the strong chemical bonding force between ions and the obvious improvement of the structural stability of the material.
Comparative example 2
Compared with the example 2, the raw material molar ratio is changed into that the proper amount of zinc acetate dihydrate (Zn (CH) is weighed according to the molar ratio of 4:0.3:3:0.333COO)2·2H2O), aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), indium trichloride tetrahydrate (InCl)3·4H2O) and stannous chloride dihydrate (SnCl)2·2H2O), and other steps are not changed, so that an AZO/ITO-LCO sample is prepared.
Under the test conditions that the charge-discharge multiplying power is 0.5C and the test voltage range is 2.75-4.5V, after 50 cycles, the capacity retention rate of the AZO/ITO-LCO sample is 71.2%.
Comparative example 3
Compared with the example 2, the raw material molar ratio is changed to that the proper amount of zinc acetate dihydrate (Zn (CH) is weighed according to the molar ratio of 9:0.7:3:0.333COO)2·2H2O), aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), indium trichloride tetrahydrate (InCl)3·4H2O) and stannous chloride dihydrate (SnCl)2·2H2O), and other steps are not changed, so that an AZO/ITO-LCO sample is prepared.
Under the test conditions that the charge-discharge multiplying power is 0.5C and the test voltage range is 2.75-4.5V, after 50 cycles, the capacity retention rate of the AZO/ITO-LCO sample is 75.2%.
Comparative example 2, comparative example 3 and example 2 changed the molar ratio of Zn and In the raw material, and thus the amounts of AZO and ITO In the clad layer, and the capacity retention rate was significantly decreased. The reason for this is that Zn and In may form more crosslinking chemical bonds at an appropriate ratio, and a stable composite clad layer may not be formed even when Zn is too much or too little.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.

Claims (4)

1.一种高电压高倍率钴酸锂正极材料的制备方法，其特征在于，包括以下步骤：1. a preparation method of high-voltage high-rate lithium cobalt oxide positive electrode material, is characterized in that, comprises the following steps: 1)制备钴酸锂材料1) Preparation of lithium cobalt oxide material 按照摩尔比Li/Co＝1.03～1.07的比例，将Li2CO3和Co3O4混合均匀,在罩式炉中进行高温反应，先在950℃下预烧4～6h，然后提高温度，1000～1100℃下继续煅烧6～14h，随炉冷却至室温，粉碎后得到预产物；将粉碎后的预产物与添加剂按比例混合均匀，900～950℃下煅烧4～7h，粉碎后即得到钴酸锂粉末；According to the molar ratio Li/Co=1.03～1.07, Li 2 CO 3 and Co 3 O 4 are mixed uniformly, and the high temperature reaction is carried out in a bell furnace. Continue calcining at 1000-1100 ℃ for 6-14 hours, cool down to room temperature with the furnace, and pulverize to obtain pre-product; mix the pulverized pre-product and additives uniformly in proportion, calcinate at 900-950 ℃ for 4-7 hours, and obtain after pulverization Lithium cobalt oxide powder; 2)采用溶胶-凝胶法制备导电氧化物包覆溶液2) Preparation of conductive oxide coating solution by sol-gel method 按照摩尔比为7:0.4:3:0.33称取二水合醋酸锌(Zn(CH3COO)2·2H2O)、九水合硝酸铝(Al(NO3)3·9H2O)，四水合三氯化铟(InCl3·4H2O)以及二水合氯化亚锡(SnCl2·2H2O)依次加入到乙醇溶液中，搅拌后加入与二水合醋酸锌等物质量的分散剂乙醇胺(NH2CH2CH2OH)，将混合物置于50℃的水浴中充分搅拌，直到得到澄清透明的溶液，冷却后在容量瓶中用乙醇定容到0.1mol/L，即为AZO/ITO复合包覆溶液，将配制好的溶液在室温下静置24h备用；According to the molar ratio of 7:0.4:3:0.33, weigh zinc acetate dihydrate (Zn(CH 3 COO) 2 ·2H 2 O), aluminum nitrate nonahydrate (Al(NO 3 ) 3 ·9H 2 O), tetrahydrate Indium trichloride (InCl 3 ·4H 2 O) and stannous chloride dihydrate (SnCl 2 ·2H 2 O) were added to the ethanol solution in turn, and after stirring, a dispersant ethanolamine ( NH 2 CH 2 CH 2 OH), put the mixture in a water bath at 50°C and stir well until a clear and transparent solution is obtained. After cooling, dilute to 0.1 mol/L with ethanol in a volumetric flask, which is AZO/ITO composite Coat the solution, and let the prepared solution stand for 24h at room temperature for later use; 3)包覆3) Coating 称取3～8g制备好的钴酸锂粉末，加入步骤2)中制得的包覆溶液，包覆溶液的加入量以包覆溶液中导电氧化物的净质量含量计，导电氧化物/钴酸锂＝0.5％～4％，在室温下充分搅拌后加热直到溶剂完全蒸发；再在500～700℃，烧结5～8h，得到包覆改性的钴酸锂正极材料。Weigh 3-8 g of the prepared lithium cobalt oxide powder, and add the coating solution prepared in step 2). Lithium oxide = 0.5% to 4%, fully stirred at room temperature and heated until the solvent is completely evaporated; then sintered at 500 to 700° C. for 5 to 8 hours to obtain a coated and modified lithium cobalt oxide cathode material. 2.根据权利要求1所述高电压高倍率钴酸锂正极材料的制备方法，其特征在于，所述添加剂为氧化镁、氢氧化镁、二氧化钛、氧化铈、三氧化二铝、氯化锆中的一种或几种。2. the preparation method of the high-voltage high-rate lithium cobalt oxide cathode material according to claim 1, wherein the additive is magnesium oxide, magnesium hydroxide, titanium dioxide, cerium oxide, aluminum oxide, zirconium chloride one or more of them. 3.根据权利要求2所述高电压高倍率钴酸锂正极材料的制备方法，其特征在于，每种所述添加剂占Li2CO3和Co3O4总质量的0.03％～0.2％。3 . The method for preparing a high voltage and high rate lithium cobalt oxide cathode material according to claim 2 , wherein each of the additives accounts for 0.03% to 0.2% of the total mass of Li 2 CO 3 and Co 3 O 4 . 4 . 4.如权利要求1-3任一项所述电压高倍率钴酸锂正极材料的制备方法制得的钴酸锂正极材料。4. The lithium cobalt oxide positive electrode material prepared by the method for preparing a high voltage lithium cobalt oxide positive electrode material according to any one of claims 1-3.
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CN111825124B (en) * 2020-06-10 2022-02-15 昆明理工大学 A method for preparing high-voltage cathode material by surface modification and regeneration of waste lithium cobalt oxide material
CN114142010B (en) * 2021-11-26 2024-05-14 天津巴莫科技有限责任公司 Magnesium oxide and cerium fluoride composite coated lithium ion battery positive electrode material and preparation method thereof
CN114105156B (en) * 2022-01-27 2022-05-27 浙江帕瓦新能源股份有限公司 Nickel-cobalt-boron precursor material, preparation method thereof and nickel-cobalt-boron positive electrode material
CN115064692B (en) * 2022-06-13 2024-11-15 天津巴莫科技有限责任公司 A composite coated lithium cobalt oxide positive electrode material and its preparation process
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CN118231604A (en) * 2023-09-26 2024-06-21 天津国安盟固利新材料科技股份有限公司 Cobalt-containing positive electrode material with multilevel structure, preparation method thereof and lithium ion battery
CN117638033B (en) * 2023-12-04 2025-10-31 中国科学院大学 Preparation method of coated and modified high-voltage lithium cobalt oxide positive electrode material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1783577A (en) * 2004-11-29 2006-06-07 潘树明 Novel method for regenerating positive material waste of lithium secondary cell
CN101436666A (en) * 2007-11-14 2009-05-20 肇庆市风华锂电池有限公司 Anode material of lithium ion cell and preparation method thereof
CN103151528A (en) * 2013-02-28 2013-06-12 天津工业大学 Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material
CN103490063A (en) * 2013-09-11 2014-01-01 中信国安盟固利电源技术有限公司 Preparation method for modified lithium cobalt oxide capable of being recycled at high cut-off voltage

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050130042A1 (en) * 2003-12-11 2005-06-16 Byd America Corporation Materials for positive electrodes of lithium ion batteries and their methods of fabrication
CN102263239B (en) * 2011-06-21 2016-02-10 深圳市本征方程石墨烯技术股份有限公司 One kind graphene coated adulterated lithium manganate composite positive pole and preparation method thereof
CN102842705B (en) * 2011-06-22 2015-03-11 清华大学 Cobalt oxide and composite material thereof, and preparation method of cobalt oxide composite material
CN103390748B (en) * 2013-08-05 2016-08-17 欧赛新能源科技股份有限公司 A kind of preparation method of alumina-coated lithium cobaltate cathode material
CN103441267A (en) * 2013-08-28 2013-12-11 欧赛新能源科技有限公司 Preparation method of titanium dioxide coated lithium cobalt oxide anode material
CN106865496A (en) * 2017-04-19 2017-06-20 中南大学 Nickel cobalt lithium aluminate cathode material of aluminium nanometer doped zinc oxide cladding and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1783577A (en) * 2004-11-29 2006-06-07 潘树明 Novel method for regenerating positive material waste of lithium secondary cell
CN101436666A (en) * 2007-11-14 2009-05-20 肇庆市风华锂电池有限公司 Anode material of lithium ion cell and preparation method thereof
CN103151528A (en) * 2013-02-28 2013-06-12 天津工业大学 Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material
CN103490063A (en) * 2013-09-11 2014-01-01 中信国安盟固利电源技术有限公司 Preparation method for modified lithium cobalt oxide capable of being recycled at high cut-off voltage

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